JPH04342556A - Tetracyanoquinodimethane double salt and its production thereof - Google Patents
Tetracyanoquinodimethane double salt and its production thereofInfo
- Publication number
- JPH04342556A JPH04342556A JP2302591A JP2302591A JPH04342556A JP H04342556 A JPH04342556 A JP H04342556A JP 2302591 A JP2302591 A JP 2302591A JP 2302591 A JP2302591 A JP 2302591A JP H04342556 A JPH04342556 A JP H04342556A
- Authority
- JP
- Japan
- Prior art keywords
- double salt
- tcnq
- acetonitrile
- tetracyanoquinodimethane
- methanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000003839 salts Chemical class 0.000 title claims abstract description 67
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 75
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000013078 crystal Substances 0.000 claims abstract description 33
- QIPOHFUODFGVHI-UHFFFAOYSA-N 2-butylisoquinolin-2-ium Chemical compound C1=CC=CC2=C[N+](CCCC)=CC=C21 QIPOHFUODFGVHI-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 abstract description 56
- 239000000203 mixture Substances 0.000 abstract description 9
- 238000003756 stirring Methods 0.000 description 14
- 239000003990 capacitor Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- -1 organic cation iodide Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- AZWDISHHPONIAX-UHFFFAOYSA-N 1-butylquinolin-1-ium Chemical compound C1=CC=C2[N+](CCCC)=CC=CC2=C1 AZWDISHHPONIAX-UHFFFAOYSA-N 0.000 description 1
- IHKFGLYNWLIHOK-UHFFFAOYSA-N 1-dodecylquinolin-1-ium Chemical compound C1=CC=C2[N+](CCCCCCCCCCCC)=CC=CC2=C1 IHKFGLYNWLIHOK-UHFFFAOYSA-N 0.000 description 1
- BDWQEVUSICVXST-UHFFFAOYSA-N 1-octylquinolin-1-ium Chemical compound C1=CC=C2[N+](CCCCCCCC)=CC=CC2=C1 BDWQEVUSICVXST-UHFFFAOYSA-N 0.000 description 1
- HJLJXUSVKKDAJT-UHFFFAOYSA-N 1-propylquinolin-1-ium Chemical compound C1=CC=C2[N+](CCC)=CC=CC2=C1 HJLJXUSVKKDAJT-UHFFFAOYSA-N 0.000 description 1
- ZFCMISKWVFUWHP-UHFFFAOYSA-N 2-dodecylisoquinolin-2-ium Chemical compound C1=CC=CC2=C[N+](CCCCCCCCCCCC)=CC=C21 ZFCMISKWVFUWHP-UHFFFAOYSA-N 0.000 description 1
- NILAICYBMURYBA-UHFFFAOYSA-N 2-octylisoquinolin-2-ium Chemical compound C1=CC=CC2=C[N+](CCCCCCCC)=CC=C21 NILAICYBMURYBA-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- NODRFQNUEKRXRF-UHFFFAOYSA-N 2-propylisoquinolin-2-ium Chemical compound C1=CC=CC2=C[N+](CCC)=CC=C21 NODRFQNUEKRXRF-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-O hydron;quinoline Chemical compound [NH+]1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-O 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- AWJUIBRHMBBTKR-UHFFFAOYSA-N iso-quinoline Natural products C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 1
- AWJUIBRHMBBTKR-UHFFFAOYSA-O isoquinolin-2-ium Chemical compound C1=[NH+]C=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-O 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、テトラシアノキノジメ
タン（以下ＴＣＮＱと略す）複塩とその製法に関する。
該ＴＣＮＱ複塩は微粉飛散せず、触ったとき砂状の感触
を呈する取り扱いが容易な柱状結晶であり、有機半導体
として、アルミ電解コンデンサー、帯電防止膜、感熱素
子等に使うことができ、他の用途への適用も期待されて
いる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tetracyanoquinodimethane (hereinafter abbreviated as TCNQ) double salt and a method for producing the same. The TCNQ double salt is a columnar crystal that does not scatter fine particles and has a sand-like feel when touched, and is easy to handle.As an organic semiconductor, it can be used in aluminum electrolytic capacitors, antistatic films, heat-sensitive elements, etc. It is also expected to be applied to other uses.
【０００２】0002
【従来技術】ＴＣＮＱ複塩の合成については、下式（１
）（２）に示す方法等が知られている〔Ｊ．Ａｍ．Ｃｈ
ｅｍ．Ｓｏｃ．，８４ ３３７４〜３３８７（１９６
２）〕。[Prior Art] Regarding the synthesis of TCNQ double salt, the following formula (1
) (2) and the like are known [J. Am. Ch
em. Soc. , 84 3374-3387 (196
2)].
【０００３】0003
【数１】[Math 1]
【０００４】一般的には次のような２法が報告されてい
る。すなわち、ＴＣＮＱをアセトニトリルに加熱溶解し
、これに有機カチオンアイオダイド〔Ｍ（＋）Ｉ（−）
〕を溶解したアセトニトリル溶液を滴下、還流を行い、
冷却後析出した結晶を濾別することによりＴＣＮＱ複塩
を取得する方法またはＴＣＮＱをアセトニトリルに加熱
溶解し、ＬｉＴＣＮＱのメタノール溶液を滴下し、さら
に有機カチオンブロミド〔Ｍ（＋）Ｂｒ（−）〕を溶解
したアセトニトリル溶液を適下、還流を行い、冷却後析
出した結晶を濾別することにより、ＴＣＮＱ複塩を取得
する方法である。Generally, the following two methods have been reported. That is, TCNQ is heated and dissolved in acetonitrile, and organic cation iodide [M(+)I(-)
] was added dropwise and refluxed.
A method of obtaining TCNQ double salt by filtering out precipitated crystals after cooling, or dissolving TCNQ in acetonitrile by heating, dropping a methanol solution of LiTCNQ, and further adding organic cation bromide [M(+)Br(-)]. In this method, the dissolved acetonitrile solution is dripped and refluxed, and after cooling, the precipitated crystals are separated by filtration to obtain TCNQ double salt.
【０００５】これらの方法によって取得されるＴＣＮＱ
複塩結晶は、飛散しやすい綿状の外観を示す嵩密度（Ａ
ＢＤ）０．１０〜０．１５の針状結晶（図３参照）であ
る。またここで得られるＴＣＮＱ複塩は不純物を含むた
め、アセトニトリルなどの有機溶媒から再結晶操作を繰
り返したり（特開昭５８−１９１４１４）、メタノール
中で熱洗浄を行うことも（特開昭６４−７０４７１）報
告されている。しかし、それらの報文中、結晶形状が柱
状に変化し、感触が砂状で、高い嵩密度の錯体を得る方
法については何等記載されていない。[0005] TCNQ obtained by these methods
Double salt crystals have a bulk density (A
BD) 0.10 to 0.15 needle-like crystals (see Figure 3). In addition, since the TCNQ double salt obtained here contains impurities, it may be repeatedly recrystallized from an organic solvent such as acetonitrile (Japanese Patent Application Laid-open No. 191414-1982), or thermally washed in methanol (Japanese Patent Application Laid-open No. 64-1989). 70471) has been reported. However, none of these reports describes a method for obtaining a complex with a columnar crystal shape, a sand-like texture, and a high bulk density.
【０００６】ＴＣＮＱの１つの重要な用途として、固体
電解コンデンサの製造における使用である。固体電解コ
ンデンサは、通常電解コンデンサの容器であるアルミニ
ウム等の金属容器に必要量のＴＣＮＱ複塩を充填し、Ｔ
ＣＮＱ複塩を加熱溶融し、これにコンデンサ素子を浸漬
、冷却後、容器を閉じることにより行われている。この
とき、容器にすりきり一杯のＴＣＮＱ複塩を入れると、
丁度適量になるような嵩密度のＴＣＮＱ複塩があればコ
ンデンサの製造上極めて有利である。ところが、前記の
公知の方法で製造したＴＣＮＱ複塩の結晶は綿状でかつ
嵩密度が０．１０〜０．２といった低いものであるため
、アルミニウム容器内にＴＣＮＱ複塩を充填する操作が
煩雑であり、工程上のネックになっており、取り扱いや
すいＴＣＮＱ複塩の結晶の出現がのぞまれていた。One important application of TCNQ is in the manufacture of solid electrolytic capacitors. Solid electrolytic capacitors are manufactured by filling the required amount of TCNQ double salt into a metal container such as aluminum, which is normally used as a container for electrolytic capacitors.
This is carried out by heating and melting the CNQ double salt, immersing the capacitor element in it, and closing the container after cooling. At this time, if you put a cup of TCNQ double salt into the container,
If there is a TCNQ double salt having just the right amount of bulk density, it will be extremely advantageous in the production of capacitors. However, since the crystals of TCNQ double salt produced by the above-mentioned known method are flocculent and have a low bulk density of 0.10 to 0.2, the operation of filling TCNQ double salt into an aluminum container is complicated. This has become a bottleneck in the process, and the emergence of TCNQ double salt crystals that are easy to handle has been desired.
【０００７】[0007]
【発明が解決しようとする課題点】従来から知れている
綿状または粉末状の如き外観を示す嵩密度０．１０〜０
．１５ｇ／ｍｌの針状結晶は、取扱い時に空気中に飛散
し易く、皮膚に付着したり、呼吸器を通して吸入する恐
れがあるなど、衛生上、また取り扱い上問題であった。[Problems to be Solved by the Invention] A bulk density of 0.10 to 0, which has a cotton-like or powder-like appearance, which has been known in the past.
．． Needle-like crystals of 15 g/ml tend to scatter into the air when handled, causing problems in terms of hygiene and handling, such as the possibility of them adhering to the skin or being inhaled through the respiratory tract.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、取扱いの
優れたＴＣＮＱ複塩結晶を製造する方法について研究を
重ねた結果、アセトニトリルを含むＴＣＮＱ複塩を、メ
タノールまたはアセトニトリルとメタノールの混合液中
、スラリー状態で攪拌することにより高嵩密度で砂状の
ＴＣＮＱ複塩が取得できることを見出し、本発明に到達
した。[Means for Solving the Problems] As a result of repeated research on a method for producing TCNQ double salt crystals that are easy to handle, the present inventors have developed a method for producing TCNQ double salt crystals containing acetonitrile in methanol or a mixture of acetonitrile and methanol. It was discovered that a sandy TCNQ double salt with high bulk density can be obtained by stirring in a slurry state, and the present invention was achieved based on this finding.
【０００９】本発明の１つは嵩密度０．３１〜０．５０
ｇ／ｍｌ、好ましくは０．３３〜０．４５ｇ／ｍｌの柱
状結晶よりなるテトラシアノキノジメタン複塩に関する
。One of the aspects of the present invention is that the bulk density is 0.31 to 0.50.
The present invention relates to a tetracyanoquinodimethane double salt consisting of columnar crystals of g/ml, preferably 0.33 to 0.45 g/ml.
【００１０】本発明の他の１つは、アセトニトリルを含
む針状テトラシアノキノジメタン複塩結晶を、メタノー
ルまたはアセトニトリルとメタノールの混合液と混合し
、スラリー状態で攪拌することを特徴とする前記テトラ
シアノキノジメタン複塩結晶の製法に関する。Another aspect of the present invention is that the acicular tetracyanoquinodimethane double salt crystals containing acetonitrile are mixed with methanol or a mixture of acetonitrile and methanol, and the mixture is stirred in a slurry state. This invention relates to a method for producing tetracyanoquinodimethane double salt crystals.
【００１１】本発明で高嵩密度複塩結晶を取得できるＴ
ＣＮＱ複塩としては、Ｎ位を置換したキノリン、イソキ
ノリン等のＴＣＮＱ複塩が挙げられる。なおＮ位の置換
基としては水素、Ｃ１〜Ｃ１２（炭素数１〜１２）のア
ルキル基（例えばメチル基、エチル基、プロピル基、ブ
チル基、ペンチル基、ヘキシル基、オクチル基、ドデシ
ル基）、アラルキル基（例えばフェネチル基）、アルケ
ニル基の様な炭化水素基である。具体的には、キノリニ
ウムＴＣＮＱ複塩、イソキノリニウムＴＣＮＱ複塩、Ｎ
−プロピルキノリニウムＴＣＮＱ複塩、Ｎ−プロピルイ
ソキノリニウムＴＣＮＱ複塩、Ｎ−ブチルキノリニウム
ＴＣＮＱ複塩、Ｎ−ブチルイソキノリニウムＴＣＮＱ複
塩、Ｎ−オクチルキノリニウムＴＣＮＱ複塩、Ｎ−オク
チルイソキノリニウムＴＣＮＱ複塩、Ｎ−ドデシルキノ
リニウムＴＣＮＱ複塩、Ｎ−ドデシルイソキノリニウム
ＴＣＮＱ複塩等である。[0011] T that can obtain high bulk density double salt crystals according to the present invention
Examples of the CNQ double salt include TCNQ double salts such as quinoline and isoquinoline substituted at the N-position. In addition, as a substituent at the N position, hydrogen, a C1 to C12 (C1 to C12) alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group), Hydrocarbon groups such as aralkyl groups (eg phenethyl groups) and alkenyl groups. Specifically, quinolinium TCNQ double salt, isoquinolinium TCNQ double salt, N
-Propylquinolinium TCNQ double salt, N-propylisoquinolinium TCNQ double salt, N-butylquinolinium TCNQ double salt, N-butylisoquinolinium TCNQ double salt, N-octylquinolinium TCNQ double salt , N-octylisoquinolinium TCNQ double salt, N-dodecylquinolinium TCNQ double salt, N-dodecylisoquinolinium TCNQ double salt, and the like.
【００１２】針状ＴＣＮＱ複塩結晶中に含まれるアセト
ニトリルの量は、取得を目的とするＴＣＮＱ複塩の嵩密
度に応じて、ＴＣＮＱ複塩の１〜５０重量％、好ましく
は５〜４０重量％の範囲の中から選ばれる。The amount of acetonitrile contained in the acicular TCNQ double salt crystals is 1 to 50% by weight, preferably 5 to 40% by weight of the TCNQ double salt, depending on the bulk density of the TCNQ double salt to be obtained. selected from within the range.
【００１３】アセトニトリルを含む針状ＴＣＮＱ複塩結
晶と混合するアセトニトリルとメタノールの混合液の組
成は、アセトニトリル濃度５０重量％以下、好ましくは
２５重量％以下である。The composition of the mixture of acetonitrile and methanol to be mixed with the acicular TCNQ double salt crystals containing acetonitrile is such that the acetonitrile concentration is 50% by weight or less, preferably 25% by weight or less.
【００１４】また、アセトニトリルを含む針状ＴＣＮＱ
複塩結晶とメタノールまたはメタノールとアセトニトリ
ル混合液との混合は、スラリー濃度１〜４０重量％、好
ましくは１０〜３０重量％の濃度でＴＣＮＱ複塩結晶が
攪拌できる範囲で選ばれる。[0014] Also, acicular TCNQ containing acetonitrile
The mixing of the double salt crystals and methanol or methanol and acetonitrile mixture is selected within a range where the TCNQ double salt crystals can be stirred at a slurry concentration of 1 to 40% by weight, preferably 10 to 30% by weight.
【００１５】本発明の方法は、常圧、加圧どちらでもよ
いが、操作上の容易さから、常圧でメタノールの沸点以
下の温度で行なうのが好ましい。本発明においては−１
０〜６５℃、好ましくは４０〜６５℃の中から選ばれた
温度で、メタノールまたはメタノールとアセトニトリル
の混合物と、アセトニトリルを含むＴＣＮＱ複塩をスラ
リー状態で攪拌し、一定時間同様の攪拌下、そのままの
温度を保つかまたは、昇温していくことによって熟成す
る。[0015] The method of the present invention may be carried out at normal pressure or under elevated pressure, but for ease of operation, it is preferably carried out at normal pressure and at a temperature below the boiling point of methanol. In the present invention -1
Methanol or a mixture of methanol and acetonitrile and TCNQ double salt containing acetonitrile are stirred in a slurry state at a temperature selected from 0 to 65°C, preferably 40 to 65°C, and left as is for a certain period of time under similar stirring. Ripening occurs by maintaining or increasing the temperature.
【００１６】熟成時間は１０〜３００分、好ましくは３
０〜１２０分である。攪拌速度は使用する反応器の形状
、使用する攪拌羽根の形状によって変わってくるが、攪
拌等によって、スラリーの全体または一部を流動させて
おくことは本発明にとって必要である。[0016] Aging time is 10 to 300 minutes, preferably 3
It is 0 to 120 minutes. Although the stirring speed varies depending on the shape of the reactor used and the shape of the stirring blade used, it is necessary for the present invention to keep the slurry in whole or in part fluidized by stirring or the like.
【００１７】[0017]
【実施例】次に実施例により本発明をさらに具体的に説
明する。但し本発明はこれらの実施例により制限される
ものではない。
実施例１
フラスコ中に９．４ｇのアセトニトリルと、１６０ｇの
メタノールの混合液を仕込み、５０℃で攪拌した。ここ
に１５重量％のアセトニトリルを含む針状Ｎ−ブチルイ
ソキノリニウムＴＣＮＱ複塩７０．６ｇを３０分かけて
加えた。１．５時間、５０℃を保ったまま攪拌の後冷却
し、２５℃で該ＴＣＮＱ複塩を濾別、乾燥したところ、
柱状結晶で嵩密度（ＡＢＤ）０．３５のＮ−ブチルイソ
キノリニウムＴＣＮＱ複塩５６．８ｇを得た。この結晶
のＸ線回折図を図２に示す。図中○印は図４との主な相
違点に相当する。EXAMPLES Next, the present invention will be explained in more detail with reference to Examples. However, the present invention is not limited to these Examples. Example 1 A mixed solution of 9.4 g of acetonitrile and 160 g of methanol was placed in a flask and stirred at 50°C. 70.6 g of acicular N-butylisoquinolinium TCNQ double salt containing 15% by weight of acetonitrile was added thereto over 30 minutes. After stirring for 1.5 hours while maintaining the temperature at 50°C, the TCNQ double salt was filtered and dried at 25°C.
56.8 g of N-butylisoquinolinium TCNQ double salt having columnar crystals and a bulk density (ABD) of 0.35 was obtained. The X-ray diffraction pattern of this crystal is shown in FIG. The ○ marks in the figure correspond to the main differences from FIG. 4.
【００１８】実施例２
フラスコ中に１９０．６ｇのメタノールを仕込み、５５
℃で攪拌した。ここに２６重量％のアセトニトリルを含
む針状Ｎ−ブチルイソキノリニウムＴＣＮＱ複塩９７．
２ｇを３０分かけて加えた。１時間、５５℃を保ったま
ま攪拌の後冷却し、２５℃で該ＴＣＮＱ複塩を濾別、乾
燥したところ、柱状結晶で（図１参照）嵩密度（ＡＢＤ
）０．３５のＮ−ブチルイソキノリニウムＴＣＮＱ複塩
７０．６ｇを得た。Example 2 190.6 g of methanol was charged into a flask, and 55 g of methanol was charged.
Stir at ℃. Acicular N-butylisoquinolinium TCNQ double salt containing 26% by weight of acetonitrile 97.
2g was added over 30 minutes. After stirring for 1 hour while maintaining the temperature at 55°C, the TCNQ double salt was filtered and dried at 25°C, and the bulk density (ABD
) 70.6 g of N-butylisoquinolinium TCNQ double salt of 0.35 was obtained.
【００１９】実施例３
フラスコ中に３９．４ｇのアセトニトリルと、３０８ｇ
のメタノールの混合液を仕込み、３０℃で撹拌した。こ
こに１０重量％のアセトニトリルを含む針状Ｎ−ブチル
イソキノリニウムＴＣＮＱ複塩１３２ｇを３０分かけて
加えた。撹拌下１．５時間かけて６５℃まで昇温した後
冷却し、２５℃で該ＴＣＮＱ複塩を濾別、乾燥したとこ
ろ、柱状結晶で嵩密度（ＡＢＤ）０．４４のＮ−ブチル
イソキノリニウムＴＣＮＱ複塩１１４ｇを得た。Example 3 In a flask, 39.4 g of acetonitrile and 308 g
A mixed solution of methanol was charged and stirred at 30°C. 132 g of acicular N-butylisoquinolinium TCNQ double salt containing 10% by weight of acetonitrile was added thereto over 30 minutes. The temperature was raised to 65°C over 1.5 hours with stirring, then cooled, and the TCNQ double salt was filtered and dried at 25°C. 114 g of Norinium TCNQ double salt was obtained.
【００２０】比較例１
フラスコ中に９．４ｇのアセトニトリルと、１６０ｇの
メタノールの混合液を仕込み、５０℃で攪拌した。ここ
に針状Ｎ−ブチルイソキノリニウムＴＣＮＱ複塩６０．
０ｇを３０分かけて加えた。１．５時間、５０℃を保っ
たまま撹拌の後冷却し、２５℃で該ＴＣＮＱ複塩を濾別
、乾燥したところ、嵩密度（ＡＢＤ）０．２５の粉末状
Ｎ−ブチルイソキノリニウムＴＣＮＱ複塩５６．８ｇを
得た。Comparative Example 1 A mixture of 9.4 g of acetonitrile and 160 g of methanol was placed in a flask and stirred at 50°C. Here, acicular N-butylisoquinolinium TCNQ double salt 60.
0g was added over 30 minutes. After stirring for 1.5 hours while maintaining the temperature at 50°C, the TCNQ double salt was filtered and dried at 25°C. 56.8 g of TCNQ double salt was obtained.
【００２１】比較例２
フラスコ中に１９０．６ｇのメタノールを仕込み、５５
℃で攪拌した。ここに針状Ｎ−ブチルイソキノリニウム
ＴＣＮＱ複塩７２．０ｇを３０分かけて加えた。１時間
、５５℃を保ったまま攪拌の後冷却し、２５℃で該ＴＣ
ＮＱ複塩を濾別、乾燥したところ、嵩密度（ＡＢＤ）０
．１５の針状Ｎ−ブチルイソキノリニウムＴＣＮＱ複塩
５６．８ｇを得た。この結晶のＸ線回折図を図４に示す
。Comparative Example 2 190.6g of methanol was charged in a flask, and 55g of methanol was charged.
Stir at ℃. 72.0 g of acicular N-butylisoquinolinium TCNQ double salt was added thereto over 30 minutes. After stirring for 1 hour while maintaining the temperature at 55°C, the TC was cooled at 25°C.
When the NQ double salt was filtered and dried, the bulk density (ABD) was 0.
．． 56.8 g of acicular N-butylisoquinolinium TCNQ double salt of No. 15 was obtained. An X-ray diffraction diagram of this crystal is shown in FIG.
【００２２】比較例３
フラスコ中に１９０．６ｇのメタノールを仕込み、５５
℃で攪拌した。ここに２６重量％のジメチルホルムアミ
ドを含む針状Ｎ−ブチルイソキノリニウムＴＣＮＱ複塩
９７．２ｇを３０分かけて加えた。２時間、５５℃を保
ったまま攪拌の後冷却し、２５℃で該ＴＣＮＱ複塩を濾
別、乾燥したところ、嵩密度（ＡＢＤ）０．２８の粉末
状Ｎ−ブチルイソキノリニウムＴＣＮＱ複塩７０．６ｇ
を得た。Comparative Example 3 190.6g of methanol was charged in a flask, and 55g of methanol was charged.
Stir at ℃. 97.2 g of acicular N-butylisoquinolinium TCNQ double salt containing 26% by weight of dimethylformamide was added thereto over 30 minutes. After stirring for 2 hours while maintaining the temperature at 55°C, the TCNQ double salt was filtered and dried at 25°C. 70.6g salt
I got it.
【００２３】[0023]
【発明の効果】本発明の方法によるＴＣＮＱ複塩は、嵩
密度が０．３１〜０．５０ｇ／ｍｌで飛散しにくいため
、皮膚に付着したり吸入する危険が減り、衛生的な作業
を行うことが可能であり、また秤量が容易となるなど取
り扱いが容易である。Effect of the invention: The TCNQ double salt produced by the method of the present invention has a bulk density of 0.31 to 0.50 g/ml and is difficult to scatter, reducing the risk of adhesion to the skin or inhalation, allowing for sanitary work. It is also easy to handle, such as easy weighing.
【図１】本発明の柱状結晶の１例を示す顕微鏡写真であ
る。FIG. 1 is a micrograph showing an example of a columnar crystal of the present invention.
【図２】本発明の柱状結晶のＸ線回折図である。FIG. 2 is an X-ray diffraction diagram of a columnar crystal of the present invention.
【図３】従来方法による針状結晶の１例を示す顕微鏡写
真である。FIG. 3 is a micrograph showing an example of needle-shaped crystals produced by a conventional method.
【図４】従来方法による針状結晶のＸ線回折図である。FIG. 4 is an X-ray diffraction diagram of needle-like crystals obtained by a conventional method.
Claims (4)
柱状結晶よりなるテトラシアノキノジメタン複塩。Claim 1: A tetracyanoquinodimethane double salt consisting of columnar crystals with a bulk density of 0.31 to 0.50 g/ml.
柱状結晶よりなるＮ−ブチルイソキノリニウム テト
ラシアノキノジメタン複塩。2. N-butylisoquinolinium tetracyanoquinodimethane double salt consisting of columnar crystals with a bulk density of 0.31 to 0.50 g/ml.
ノキノジメタン複塩結晶とメタノールまたはアセトニト
リルとメタノールの混合液とを混合し、スリラー状態で
攪拌することを特徴とする請求項１記載のテトラシアノ
キノジメタン複塩結晶の製法。3. The tetracyanoquinodimethane according to claim 1, wherein the acicular tetracyanoquinodimethane double salt crystals containing acetonitrile and methanol or a mixed solution of acetonitrile and methanol are mixed and stirred in a thriller state. Method for producing dimethane double salt crystals.
ルイソキノリニウムテトラシアノキノジメタンである請
求項３記載の製法。4. The method according to claim 3, wherein the tetracyanoquinodimethane is N-butylisoquinolinium tetracyanoquinodimethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2302591A JPH04342556A (en) | 1991-01-23 | 1991-01-23 | Tetracyanoquinodimethane double salt and its production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2302591A JPH04342556A (en) | 1991-01-23 | 1991-01-23 | Tetracyanoquinodimethane double salt and its production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04342556A true JPH04342556A (en) | 1992-11-30 |
Family
ID=12098943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2302591A Pending JPH04342556A (en) | 1991-01-23 | 1991-01-23 | Tetracyanoquinodimethane double salt and its production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04342556A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7569701B2 (en) | 2002-04-10 | 2009-08-04 | Nippon Zoki Pharmaceutical Co., Ltd. | Crystal form of 5-hydroxy-1-methylimidazolidin-2,4-dione |
-
1991
- 1991-01-23 JP JP2302591A patent/JPH04342556A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7569701B2 (en) | 2002-04-10 | 2009-08-04 | Nippon Zoki Pharmaceutical Co., Ltd. | Crystal form of 5-hydroxy-1-methylimidazolidin-2,4-dione |
| US7858806B2 (en) | 2002-04-10 | 2010-12-28 | Nippon Zoki Pharmaceutical Co., Ltd. | Crystal form of 5-hydroxy-1-methylhydantoin |
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